Manufacturing of fuel cell membrane electrode assemblies incorporating photocurable cationic crosslinkable resin gasket

ABSTRACT

A first transport system moves a web comprising a subgasketed CCM layer and an application system applies a crosslinkable resin to at least a subgasketed portion of the subgasketed CCM layer. The crosslinkable resin preferably comprises a photocurable cationic crosslinkable resin. A first curing apparatus subjects an exposed surface of the crosslinkable resin to a photo curing process to initiate curing of the crosslinkable resin. A second transport system moves a GDL into adhering contact with a partially cured exposed surface of the crosslinkable resin of the CCM layer so as to form an MEA layer. A second curing apparatus subjects the GDL, partially cured crosslinkable resin, and CCM layer structure to a thermal curing process to substantially complete curing of the crosslinkable resin. A converting system is configured to receive the MEA layer and produce a plurality of discrete MEAs from the MEA layer.

FIELD OF THE INVENTION

The present invention relates generally to fuel cell assemblies andmethods of assembly that employ a dual-purpose crosslinkable resingasket of an electrode membrane assembly and, more particularly, to aphotocurable cationic crosslinkable resin gasket for use in an electrodemembrane assembly.

BACKGROUND OF THE INVENTION

A typical fuel cell system includes a power section in which one or morefuel cells generate electrical power. A fuel cell is an energyconversion device that converts hydrogen and oxygen into water,producing electricity and heat in the process. Each fuel cell unit mayinclude a proton exchange member (PEM) with gas diffusion layers oneither side of the proton exchange member. Anode and cathode catalystlayers are respectively positioned between the gas diffusion layers andthe PEM. This unit is referred to as a membrane electrode assembly(MEA). Separator plates (also referred to herein and flow field platesor bipolar plates) are respectively positioned on the outside of the gasdiffusion layers of the membrane electrode assembly. This type of fuelcell is often referred to as a PEM fuel cell.

The reaction in a single MEA typically produces less than one volt.Therefore, to obtain operating voltages useful in most applications, aplurality of the MEAs may be stacked and electrically connected inseries to achieve a desired voltage. Electrical current is collectedfrom the fuel cell stack and used to drive a load. Fuel cells may beused to supply power for a variety of applications, ranging fromautomobiles to laptop computers.

The efficiency of the fuel cell power system depends on the flow ofreactant gases across the surfaces of the MEA as well as the integrityof the various contacting and sealing interfaces within individual fuelcells of the fuel cell stack. Such contacting and sealing interfacesinclude those associated with the transport of fuels, coolants, andeffluents within and between fuel cells of the stack. Proper sealing offuel cell components and assemblies within a fuel cell stack is criticalto ensure efficient operation of the fuel cell system.

SUMMARY OF THE INVENTION

Embodiments of the invention are directed to fuel cell subassemblies andmethods and apparatuses for manufacturing fuel cell subassemblies.Embodiments are directed to methods of making fuel cell membraneelectrode assemblies via a roll-to-roll process. Methods of theinvention involve transporting a web comprising a subgasketed catalystcoated membrane layer and applying a crosslinkable resin to at least asubgasketed portion of the subgasketed CCM layer. The crosslinkableresin preferably comprises a photocurable cationic crosslinkable resin.An exposed surface of the crosslinkable resin is subjected to a photocuring process to initiate curing of the crosslinkable resin. The photoexposure process is terminated while the crosslinkable resin continuesto cure in a partially cured state, preferably even in the absence ofadditional light. A web comprising a gas diffusion layer (GDL) istransported into adhering contact with a partially cured exposed surfaceof the crosslinkable resin of the CCM layer so as to form an MEA layer.The GDL, partially cured crosslinkable resin, and CCM layer structuremay be subjected to a thermal curing process to substantially completecuring of the crosslinkable resin. Subsequent to substantial completionof crosslinkable resin curing, discrete MEAs may be produced from theMEA layer.

Embodiments of the invention are directed to a fuel cell MEA comprisinga CCM having a first surface and a second surface. The first surface ofthe CCM includes an anode catalyst layer and the second surface of theCCM includes a cathode catalyst layer. A subgasket is provided about aperipheral region of the CCM on the first and second surfaces. Acrosslinked resin is provided on at least the subgasket of the first andsecond CCM surfaces. The crosslinked resin preferably comprises aphotocurable cationic crosslinkable resin. A GDL is adheringly sealed tothe subgasket of the first and second CCM surfaces via the crosslinkedresin.

Embodiments of the invention are directed to an apparatus for producingfuel cell MEAs. An apparatus of the invention includes a first transportsystem configured to move a web comprising a subgasketed CCM layer andan application system configured to apply a crosslinkable resin to atleast a subgasketed portion of the subgasketed CCM layer. Thecrosslinkable resin preferably comprises a photocurable cationiccrosslinkable resin. A first curing apparatus is configured to subjectan exposed surface of the crosslinkable resin to a photo curing processto initiate curing of the crosslinkable resin. A second transport systemis configured to move a GDL into adhering contact with a partially curedexposed surface of the crosslinkable resin of the CCM layer so as toform an MEA layer. A second curing apparatus may be employed andconfigured to subject the GDL, partially cured crosslinkable resin, andCCM layer structure to a thermal curing process to substantiallycomplete curing of the crosslinkable resin. A converting system isconfigured to receive the MEA layer and produce a plurality of discreteMEAs from the MEA layer.

The above summary of the present invention is not intended to describeeach embodiment or every implementation of the present invention.Advantages and attainments, together with a more complete understandingof the invention, will become apparent and appreciated by referring tothe following detailed description and claims taken in conjunction withthe accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an illustration of a fuel cell and its constituent layers;

FIG. 2 provides an exploded diagram of a fuel cell includingdual-purpose crosslinkable resin gaskets configured in accordance withembodiments of the present invention;

FIG. 3 provides an exploded diagram of a fuel cell stack that includesunipolar and bipolar flow field plates and dual-purpose crosslinkableresin gaskets configured in accordance with embodiments of theinvention;

FIG. 4A-4F are cross sectional schematics of an MEA employing acrosslinkable resin gasket at various stages of fabrication inaccordance with embodiments of the invention;

FIG. 5 is a block diagram of an apparatus for producing an MEA web anddiscrete MEAs from the MEA web fabricated in accordance with aroll-to-roll process according to embodiments of the invention;

FIG. 6 shows an apparatus for producing an MEA web and discrete MEAsfrom the MEA web fabricated in accordance with a roll-to-roll processaccording to embodiments of the invention; and

FIG. 7 shows an apparatus for producing an MEA web and discrete MEAsfrom the MEA web fabricated in accordance with a roll-to-roll processaccording to embodiments of the invention.

While the invention is amenable to various modifications and alternativeforms, specifics thereof have been shown by way of example in thedrawings and will be described in detail. It is to be understood,however, that the intention is not to limit the invention to theparticular embodiments described. On the contrary, the intention is tocover all modifications, equivalents, and alternatives falling withinthe scope of the invention as defined by the appended claims.

DETAILED DESCRIPTION OF VARIOUS EMBODIMENTS

In the following description of the illustrated embodiments, referenceis made to the accompanying drawings that form a part hereof, and inwhich is shown by way of illustration, various embodiments in which theinvention may be practiced. It is to be understood that otherembodiments may be utilized and structural changes may be made to theillustrated embodiments without departing from the scope of the presentinvention.

Embodiments of the invention are directed to a roll-to-rollmanufacturing process to obtain membrane electrode assemblies thatemploy a crosslinkable resin that serves as both a gasket for sealingand as an adhesive for attaching a gas diffusion layer. Embodiments ofthe invention utilize a series of processes to coat a subgasketedcatalyst coated membrane with a crosslinkable resin, partially cure thecrosslinkable resin, attach a GDL to the subgasketed CCM, complete thecrosslinkable resin cure, and produce discrete MEAs. Embodiments of theinvention employ a crosslinkable resin that has a multi-stage curingproperty, wherein the crosslinkable resin remains in a partially curedstate during which the crosslinkable resin is tacky, and then progressesto a fully cured stage. Crosslinkable resins particularly well suitedfor use in roll-to-roll manufacturing processes of the present inventioninclude photocurable crosslinkable resins, such as photocurable cationiccrosslinkable resins.

Processes of the invention find particular utility in the production ofpolymer electrolyte fuel cells, specifically as a means to enablehigh-volume, roll-to-roll manufacturing of MEAs with a crosslinkableresin gasket seal on the MEA. By utilizing the crosslinkable resinsimultaneously as a seal and as an adhesive for attaching GDLs, MEAs canbe manufactured via high speed, roll-to-roll processing.

Conventional MEA fabrication methodologies for attaching a GDL to a CCMtypically involve cutting the CCM from a web to make a discrete part orassembling the CCM as a discrete part from piece parts. A discrete GDLis situated on both sides of a CCM and bonded to the CCM using a heated,static press. Conventional methodologies for attaching a seal to the MEAtypically involve cutting the MEA from a web to make a discrete part orassembling the MEA as a discrete part from piece parts, applying thecrosslinkable resin to the MEA, and curing the crosslinkable resin in aheated static, press. A significant disadvantage associated with boththe conventional GDL and seal attachment approaches is that discretepart assembly is not amenable to high-volume manufacturing.

Many conventional MEA fabrication methodologies use pressure sensitiveadhesives. Such pressure sensitive adhesives typically have a low glasstransition temperature, which can cause the adhesive to ooze or creepduring processing. Other types of adhesives that have been used in MEAfabrication employ a crosslinking polymerization mechanism. Suchadhesives generally take an appreciable amount of time to set uprelative to their limited pot life, thus precluding use of suchadhesives in roll-to-roll fabrication methodologies. Conventional UVcurable adhesives are of limited use, as the GDL blocks the UV lightfrom impinging on the UV curable adhesive. In contrast to conventionalfabrication approaches, embodiments of the invention employ anmulti-stage curable crosslinkable resin that serves as both a gasket forsealing and as an adhesive for attaching a GDL, enabling production ofMEAs using high speed, roll-to-roll processing.

A dual-purpose gasket of the present invention may be incorporated infuel cell assemblies and stacks of varying types, configurations, andtechnologies. For example, a dual-purpose gasket of the presentinvention can be employed in proton exchange membrane (PEM) fuel cellassemblies. PEM fuel cells operate at relatively low temperatures, havehigh power density, can vary their output quickly to meet shifts inpower demand, and are well suited for applications where quick startupis required, such as in automobiles for example.

Although generally illustrated herein in conjunction with PEM fuelcells, a dual-purpose gasket in accordance with embodiments of theinvention may also be employed in other types of fuel cells, includingdirect methanol fuel cells (DMFC). Direct methanol fuel cells aresimilar to PEM cells in that they both use a polymer membrane as theelectrolyte. In a DMFC, however, the anode catalyst itself draws thehydrogen from liquid methanol fuel, eliminating the need for a fuelreformer.

A typical proton exchange member fuel cell is depicted in FIG. 1. Thefuel cell 110 shown in FIG. 1 includes a first flow field plate 112adjacent a first gas diffusion layer (GDL) 114. Adjacent the GDL 114 isa catalyst coated membrane (CCM) 120. A second GDL 118 is situatedadjacent the CCM 120, and a second flow field plate 119 is situatedadjacent the second GDL 118.

In operation, hydrogen fuel is introduced into the anode portion of thefuel cell 110, passing over the first flow field separator 112 andthrough the GDL 114. At the interface of the GDL 114 and the CCM 120, onthe surface of the catalyst layer 115, the hydrogen fuel is separatedinto hydrogen ions (H⁺) and electrons (e⁻).

The electrolyte membrane 116 of the CCM 120 permits only the hydrogenions or protons and water to pass through the electrolyte membrane 116to the cathode catalyst layer 113 of the fuel cell 110. The electronscannot pass through the electrolyte membrane 116 and, instead, flowthrough an external electrical circuit in the form of electric current.This current can power an electric load 117, such as an electric motor,or be directed to an energy storage device, such as a rechargeablebattery.

Oxygen flows through the second GDL 118 at the cathode side of the fuelcell 110 via the second flow field separator 119. On the surface of thecathode catalyst layer 113, oxygen, protons, and electrons combine toproduce water and heat.

Individual fuel cells, such as the fuel cell shown in FIG. 1, can becombined to form a fuel cell stack. The number of fuel cells within thestack determines the maximum voltage of the stack, and the surface areaof each of the cells determines the maximum current. The electricalpower generated by a given fuel cell stack can be determined bymultiplying the total stack voltage by total current.

Sealing fuels, coolants, and other fluids within each fuel cell in astack is critical to the efficient operation of the fuel cell stack.Dual-purpose crosslinkable resin gaskets of the present invention arepreferably deployed around the perimeter of the active area of theelectrolyte membrane. The gaskets are critical to seal against leaks inthe peripheral areas and/or edges of the electrolyte membrane and GDLs.In some configurations, a sealing system may include both dual-purposecrosslinkable resin gaskets along with other sealing arrangements.

FIG. 2 shows an exploded diagram of the components of a fuel cell thatincludes dual-purpose gaskets in accordance with embodiments of theinvention. As is shown in FIG. 2, a membrane electrode assembly (MEA)225 of the fuel cell 220 includes five component layers. An electrolytemembrane layer 222 is sandwiched between a pair of GDLs 224 and 226. Ananode catalyst layer 230 is situated between a first GDL 224 and themembrane 222, and a cathode catalyst layer 232 is situated between themembrane 222 and a second GDL 226. A dual-purpose gasket 227 is situatedbetween GDL 224 and the membrane 222, and a dual-purpose gasket 229 issituated between GDL 226 and the membrane 222.

In one configuration, a membrane layer 222 is fabricated to include ananode catalyst coating 230 on one surface and a cathode catalyst coating232 on the other surface. This structure is often referred to as acatalyst-coated membrane or CCM. The GDLs 224, 226 can be fabricated toinclude or exclude a catalyst coating. In one configuration, an anodecatalyst coating 230 can be disposed partially on the first GDL 224 andpartially on one surface of the membrane 222, and/or a cathode catalystcoating 232 can be disposed partially on the second GDL 226 andpartially on the other surface of the membrane 222.

In the particular embodiment shown in FIG. 2, MEA 225 is shownsandwiched between a first perimeter gasket 234 and a second perimetergasket 236. Adjacent the first and second perimeter gaskets 234 and 236are flow field plates 240 and 242, respectively. Each of the flow fieldplates or separators 240, 242 includes a field of fluid flow channels243 and ports through which hydrogen and oxygen feed fuels may pass.

In the configuration depicted in FIG. 2, flow field plates 240, 242 areconfigured as unipolar flow field plates, also referred to as monopolarflow field plates, in which a single MEA 225 is sandwiched therebetween.A unipolar flow field plate may comprise a separator that includes aflow field side and a cooling side. The flow field side incorporates afield of gas flow channels 243 and ports through which hydrogen oroxygen feed fuels may pass. The cooling side incorporates a coolingarrangement, such as integral cooling channels. Alternatively, thecooling side may be configured to contact a separate cooling element,such as a cooling block or bladder through which a coolant passes or aheat sink element, for example.

The edge seal systems 234, 236 provide the necessary sealing within thefuel cell to isolate the various fluid (gas/liquid) transport andreaction regions from contaminating one another and from inappropriatelyexiting the fuel cell 220, and may further provide for electricalisolation and/or hard stop compression control between the flow fieldplates 240, 242. The term “hard stop” generally refers to a nearly orsubstantially incompressible material that does not significantly changein thickness under operating pressures and temperatures. Moreparticularly, the term “hard stop” refers to a substantiallyincompressible member or layer in a membrane electrode assembly (MEA)which halts compression of the MEA at a fixed thickness or strain.

The perimeter gaskets 234, 236, may employ one or more gaskets,sub-gaskets and/or O-rings to effect sealing of the edges of the MEA 225and sealing between and around the MEA 225 and the flow field plates240, 242. In one configuration, the perimeter gaskets 234, 236 include agasket system formed from one, two or more layers of various selectedmaterials employed to provide the requisite sealing within the fuel cell220. Such materials include, for example, TEFLON, fiberglass impregnatedwith TEFLON, a variety of crosslinkable resin materials, elastomericmaterials, UV curable polymeric material, surface texture material,multi-layered composite material, sealants, and silicon material. Otherconfigurations employ an in-situ formed seal system.

In certain embodiments, a fuel cell stack may use bipolar flow fieldplates, as illustrated in FIG. 3. FIG. 3 illustrates a fuel cell stack350 which incorporates multiple MEAs 325 through employment of unipolarflow field plates 352, 354 and one or more bipolar flow field plates356. In the configuration shown in FIG. 3, a two-cell stack 350incorporates two MEAs 325 a and 325 b and a single bipolar flow fieldplate 356. MEA 325 a includes a cathode 362 a/membrane 361 a/anode 360 alayered structure sandwiched between GDLs 366 a and 364 a. Adual-purpose gasket 340 a/342 a is disposed between the cathode 362a/GDL 366 a and anode 360 a/GDL 364 a. GDL 366 a is situated adjacent aflow field end plate 352, which is configured as a unipolar flow fieldplate. GDL 364 a is situated adjacent a first flow field surface 356 aof bipolar flow field plate 356. A perimeter gasket arrangement 371 a isdeployed to provide sealing for MEA 325 a and flow field end plate 352.Perimeter gasket arrangement 372 a is deployed to provide sealing forMEA 325 and bipolar flow field plate 356.

Similarly, MEA 325 b includes a cathode 362 b/membrane 361 b/anode 360 blayered structure sandwiched between GDLs 366 b and 364 b. Adual-purpose gasket 340 b/342 b is disposed between the cathode 362b/GDL 366 b and anode 360 b/GDL 364 b. GDL 364 b is situated adjacent aflow field end plate 354, which is configured as a unipolar flow fieldplate. GDL 366 b is situated adjacent a second flow field surface 356 bof bipolar flow field plate 356. Perimeter gasket arrangements 371 b and372 b are deployed to provide sealing for MEA 325 b and flow field endplate 354 and MEA 325 and bipolar flow field plate 356, respectively.

The fuel cell and/or stack configurations shown in FIGS. 2 and 3 arerepresentative of two particular arrangements that can be implementedfor use in the context of the present invention. These arrangements areprovided for illustrative purposes only, and are not intended torepresent all possible configurations coming within the scope of thepresent invention. Rather, FIGS. 2 and 3 are intended to illustratevarious components that can be selectively incorporated into fuel cellassemblies that include dual-purpose crosslinkable resin gasketsaccording to principles of the present invention.

FIG. 4A-4C are cross sectional schematics of an MEA employing adual-purpose crosslinkable resin gasket at various stages of fabricationin accordance with embodiments of the invention. FIG. 4A shows an MEAsubstructure 400 a that includes a catalyst coated membrane 410 providedwith a subgasket 450. The CCM 410 provided with subgasketed 450 isreferred to herein as a subgasketed CCM 412. The CCM 410 includes ananode catalyst layer 420 and a cathode catalyst layer 422. Thesubgasketed CCM 412 is preferably fabricated as a web and processed toproduce an MEA web using a roll-to-roll process.

The MEA substructure 400 b shown in FIG. 4B includes a crosslinkableresin 440 provided over at least the subgasketed portion of thesubgasketed CCM 410. The crosslinkable resin 440 is preferably disposedover the subgasket 450 and a portion of the peripheral region of the CCM440. The crosslinkable resin 440 serves as a dual-purpose gasket withinthe MEA. The crosslinkable resin 440 serves as a seal for the CCM 410and as an adhesive to facilitate attachment of the gas diffusion layer460 to the subgasketed CCM 410 during MEA fabrication. FIG. 4C shows gasdiffusion layer 460 in adhering contact with the subgasketed CCM 410 viacrosslinkable resin 440. The substructure 400 c defines an MEA thatincorporates the dual-purpose crosslinkable resin gasket 440. Thesubstructures 400 d, 400 e, and 400 f illustrated in FIGS. 4D, 4E, and4F, respectively, show various configurations of an MEA thatincorporates a dual-purpose crosslinkable resin gasket 440.

The crosslinkable resin shown in the Figures is preferably one that hassufficient latency in terms of curing duration suitable for MEAsubstructure fabrication in accordance with the present invention.Suitable crosslinkable resins include those that can be employed in anMEA substructure fabrication process while in a partially cured state.In particular, suitable crosslinkable resins include those that, when ina partially cured state, are sufficiently tacky to serve as an adhesiveduring an MEA substructure fabrication process and, when cured, serve asa seal in the fabricated MEA substructure. Suitable crosslinkable resinsinclude those that have a multi-stage curing property, wherein thecrosslinkable resin remains in a partially cured state during which thecrosslinkable resin is workable and tacky, and then progresses to afully cured stage.

In some embodiments, the crosslinkable resin is photocurable, wherebycuring of the crosslinkable resin is initiated by exposure to anappropriate light source (“light” reaction), such as an ultravioletlight source, and then progresses after removing the crosslinkable resinfrom the light source (“dark” reaction). In some embodiments, thecrosslinkable resin is photocurable and thermally curable, wherebycuring of the crosslinkable resin is initiated by exposure to anappropriate light source and then accelerated (or decelerated) byadjusting the temperature of the crosslinkable resin (e.g., the ambienttemperature surrounding the crosslinkable resin).

One such crosslinkable resin is based on the reaction of a commerciallyavailable epoxy and polyol resins with a triaryl sulfonium saltinitiator. Resins based on the diglycidylether of bisphenol A (DGEBA)such as Epon 828 or Epon 1001F obtained from Shell Chemical Company andpolyols based on polycaprolatone such as Tone 301 obtained from UnionCarbide can be used in accordance with embodiments of the invention.Other suitable crosslinkable resins include monomers that arepolymerizable by a cationic mechanism. Examples of such crosslinkableresins include photocurable cationic crosslinkable resins, such aspolymerizable epoxide monomers (aromatic and cycloaliphatic basedresins) and vinyl ether monomers. Further details about these and othersuitable crosslinkable resins are provided in J. Crivello, “TheDiscovery and Development of Onium Salt Cationic Photoinitiators,”Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 37,4241-4254 (1999).

The subgasketed CCM 412 is preferably formed as a roll good web. Thesubgasketed CCM 412, as shown in FIGS. 4A-4F, includes one or moresubgaskets 450, 450′, 450″ arranged on surfaces of the CCM 412 and mayinclude an adhesive layer, such as a pressure sensitive, thermally or UVactivated adhesive layer, therebetween. For example, the adhesive layermay comprise any of the following: acrylic PSA's, rubber basedadhesives, ethylene maleic anhydride copolymers, olefin adhesives suchas copolymers of 1-octene with ethylene or propylene, nitrile basedadhesives, epoxy based adhesives, and urethane based adhesives. In otherembodiments, the adhesive layer may comprise a thermally activatedadhesive, such as Thermobond 845 (polyethylene maleate based) andThermobond 583 (nitrile rubber based).

The subgaskets 450, 450′, 450″ may comprise various types of polymermaterial, such as polyester, polyimide, polyethylene naphthalate (PEN),polyethylene telephthalate (PET) and/or other similar materials,including rigid polymeric materials that are sufficiently thin,sufficiently strong, and sufficiently compatible with the fuel cellenvironment, i.e., temperatures of 60-120° C., in the presence of water,hydrogen and/or oxygen. Layers of the subgaskets 450, 450′, 450″ neednot have identical characteristics. The characteristics of the subgasketlayers may be selected to facilitate component handling or fuel celloperation.

Roll good webs used in the formation of fuel cell components, such asMEAs and MEA subassemblies, can be produced as a roll good output fromroll good input materials (e.g., webs of fuel cell components) inaccordance with embodiments of the present invention. For example, rollgood gasketed electrolyte membrane webs, roll good gasketed CCM webs,and/or roll good gasketed MEA webs can be fabricated using a continuousassembling approach by which roll good input web materials are processedto produce a roll good output web. Output fuel cell component webs canbe wound with appropriate liner material to form a roll. In anotherapproach, the fuel cell web can be converted into individual MEAs in asubsequent step.

FIG. 5 is a block diagram of an apparatus 500 for producing an MEA weband discrete MEAs from the MEA web fabricated in accordance with aroll-to-roll process according to embodiments of the invention. Asubgasketed CCM substructure 400 a, typically provided as a roll good tothe apparatus 500, is transported to a crosslinkable resin coatingmodule 502. At the crosslinkable resin coating module 502, a layer of acrosslinkable resin is applied to the subgasketed CCM substructure 400a. The crosslinkable resin is preferably applied to cover at least thesubgasketed portion of the subgasketed CCM substructure 400 a. Thecrosslinkable resin is preferably of a type described hereinabove, suchas a photocurable cationic crosslinkable resin. Various processes may beused to apply the crosslinkable resin to the subgasketed CCMsubstructure 400 a at the crosslinkable resin coating module 502. Asuitable approach involves use of a rotary screen printing process toapply the crosslinkable resin to the subgasketed CCM substructure 400 a,such as the process described U.S. Patent Publication 2006/0078781 whichis incorporated herein by reference.

Following application of the crosslinkable resin to the subgasketed CCMsubstructure 400 a, the substructure 400 b is transported to a firstresin curing module 504. At the first resin curing module 504, curing ofthe crosslinkable resin is initiated but not completed. Rather, thecrosslinkable resin applied to the subgasketed CCM substructure 400 aexits the first resin curing module 504 in a partially cured state. Thecrosslinkable resin preferably continues to cure even in the absence oflight subsequent to the subgasketed CCM substructure 400 a exiting thefirst resin curing module 504 in the partially cured state. Thecrosslinkable resin remains workable and serves as an adhesive while inthe partially cured state.

According to some embodiments, the crosslinkable resin comprises aphotocurable cationic crosslinkable resin that is exposed to UV light atthe first resin curing module 504. A typical dose of UV light rangesfrom about 5 mJ/cm² to about 5 J/cm². Doses can be varied by varying thelinespeed of the UV processor. Treatment of the crosslinkable resin atthe first resin curing module 504 should leave the crosslinkable resinsufficiently tacky so that a GDL can be attached to the subgasketed CCMsubstructure 400 a via adhering contact between the GDL and thecrosslinkable resin. As is shown in FIG. 5, the GDL is attached to thesubgasketed CCM substructure 400 a at a GDL attachment module 506. Thesubstructure exiting the GDL attachment module 506 defines an MEA, suchas the MEA substructures 400 c-f shown in FIGS. 4A-4F.

The MEA substructure 400 c-f is advanced to a second resin curing module508, where the crosslinkable resin is subjected to additional curing.The second resin curing module 508 may provide thermal curing, forexample. It is understood that additional UV curing of the MEAsubstructure 400 c-f is not possible due to the presence of the lightblocking GDL. Hence, an additional form of curing may be needed tocomplete curing of the crosslinkable resin. The crosslinkable resin ispreferably subjected to thermal curing at the second resin curing module508 to complete curing of the crosslinkable resin. A typical duration ofthermal curing ranges from about 1 minute to about 1 day.

In some embodiments, the apparatus 500 need not include a second resincuring module 508 depending on the particular formulation of thecrosslinkable resin. For example, the rate of crosslinkable resin curingafter initiation at the first resin curing module 504 may allow for GDLattachment and substantially complete curing thereafter within anacceptable amount of time. For high volume roll-to-roll processes,however, it is believed desirable to include an additional curing moduleto facilitate accelerated curing of the crosslinkable resin. The web ofMEA substructures 400 c-f may be converted to discrete MEAs 400 g at anMEA converting module 510. The MEA converting module 510 may include arotary die cutter, a laser cutter, or a die press, for example.

FIG. 6 shows an apparatus for producing an MEA web and discrete MEAsfrom the MEA web fabricated in accordance with a roll-to-roll processaccording to embodiments of the invention. A web of subgasketed CCMsubstructure 400 a is transported from a supply roll 605 to acrosslinkable resin coating module 502. At the crosslinkable resincoating module 502, which may include a rotary screen printer, acrosslinkable resin is applied to cover at least the subgasketed portionof the subgasketed CCM substructure 400 a. The web is advanced so thatthe CCM substructure 400 a is transported to a first resin curing module504, where curing of the crosslinkable resin is initiated but notcompleted.

The web is advanced so that the subgasketed CCM substructure 400 bprovided with the partially cured crosslinkable resin is advanced to aGDL attachment module 506. A GDL web 622 is transported from a supplyroll 620 and is moved into adhering contact with the subgasketed CCMsubstructure 400 b via rollers 610 at the GDL attachment module 506. Aswas discussed previously, the partially cured crosslinkable resinremains sufficiently tacky so that the GDL adheres to the subgasketedCCM substructure 400 b. In some configurations, the GDL web, after beingbrought into adhering contacting with the subgasketed CCM substructure400 b at the GDL attachment module 506, travels with the subgasketed CCMsubstructure web and exits the GDL attachment module 506 for furtherprocessing. In other configurations, the GDL web may include a releaseliner. A stripper arrangement 615 may be used to separate the GDL fromthe release liner. A roll 625 may be used to take up the release liner.

In some embodiments, the apparatus 600 shown in FIG. 6 may be configuredto process both surfaces of the subgasketed CCM substructure 400 bsubstantially concurrently. In such embodiments, the apparatus 600employs a second GDL web transport mechanism that includes a supply roll640 that supplies a GDL web to the GDL attachment module 506. Anoptional take-up roll 645 may be employed depending on the apparatusimplementation as discussed above. In other embodiments, a first surfaceof the subgasketed CCM substructure 400 b is processed followed byprocessing of the second surface of the subgasketed CCM substructure 400b by the apparatus 600. In such embodiments, the second GDL webtransport mechanism would not be needed.

The substructure exiting the GDL attachment module 506 defines an MEA,such as the MEA substructures 400 c-f shown in FIGS. 4A-4F. The web ofMEA substructures 400 c-f is advanced to a second resin curing module508, where the crosslinkable resin is subjected to additional curing,preferably thermal curing. The web of MEA substructures 400 c-f may beconverted to discrete MEAs 400 g at an MEA converting module 510, whichmay include a rotary die cutter, a laser cutter, or a die press, forexample.

FIG. 7 shows an apparatus for producing an MEA web and discrete MEAsfrom the MEA web fabricated in accordance with a roll-to-roll processaccording to embodiments of the invention. The apparatus illustrated inFIG. 7 is configured to sequentially process first and second surfacesof a web of subgasketed CCM substructures 700 a. As is depicted in FIG.7, a web of subgasketed CCM substructures 700 a is transported to afirst crosslinkable resin coating module 802 that applies acrosslinkable resin to cover at least the subgasketed portion of thesubgasketed CCM substructures 700 a. The web is advanced so that the CCMsubstructures 700 b are transported to a first resin curing module 804,where curing of the crosslinkable resin is initiated but not completed.The web is advanced so that the subgasketed CCM substructures 700 bprovided with the partially cured crosslinkable resin are advanced to afirst GDL attachment module 806, where GDLs are moved into adheringcontact with respective subgasketed CCM substructures 700 b. The web isadvanced to a second resin curing module 808, where the crosslinkableresin is subjected to additional curing.

After exiting the second resin curing module 808, the subgasketed CCMsubstructures 700 c are separated from a release liner 801 that supportsthe subgasketed CCM substructures 700 a-c, such as by use of a stripper.The GDLs remain adhered to a release liner 803, which exposes the secondsurface of the subgasketed CCM substructures 700 c. The second surfaceof the subgasketed CCM substructures 700 b is processes in a mannersimilar to that of the first surface. The subgasketed CCM substructures700 c are transported to a second crosslinkable resin coating module 812that applies a crosslinkable resin to cover at least the subgasketedportion of the second surface of the subgasketed CCM substructures 700c. The CCM substructures 700 d are transported to a third resin curingmodule 814, where curing of the crosslinkable resin is initiated but notcompleted. The subgasketed CCM substructures 700 d provided with thepartially cured crosslinkable resin are advanced to a second GDLattachment module 816, where GDLs are moved into adhering contact withrespective subgasketed CCM substructures 700 d. The subgasketed CCMsubstructures 700 e are advanced to a fourth resin curing module 818,where the crosslinkable resin is subjected to additional curing. The webof MEA substructures 700 e may be converted to discrete MEAs 700 f at anMEA converting module 820.

Example

Experiments were performed using a UV and thermally curable epoxyformulation as a crosslinkable resin. The formulation was as follows:

Component Parts Epon 828 Epoxy resin 60 Epon 1001F High viscosity epoxy14 resin Tone 301 Polyester based polyol 26 Initiator Sulfonium salt* 5*triaryl sulfonium salt photo initiator was obtained from AcetoCorporation, Lake Success New York.

The epoxy was coated onto a 3 mil thick PEN via a Meyer rod coater. Theepoxy coating was then exposed to an H-bulb UV light source for varioustimes. After exposure to the light source, a piece of GDL was placed onthe coating. The quality of the cure was characterized over time. Afterthree days, the GDL adhesion was characterized. For all samples, themicrolayer on the GDL fragmented when removing the GDL from the epoxy,indicating that the adhesive strength of the epoxy is sufficient toattach the GDL. In addition to measuring GDL adhesion after three days,the quality of the epoxy cure under the GDL was characterized before andafter placing in an oven at 110 C for 15 minutes. Table 1 belowsummarizes the results of the experiments.

TABLE 1 Sample Sample Sample Sample 1 2 Sample 3 4 5 Set Line Speed, fpm10 20 30 40 50 Actual line Speed, fpm 6.5 13 19.5 26 32.5 Cure at t = 0min 5 4 3 2 2 Cure at t~5 min 6 3 3 Cure at t~10 min 8 7 6 4 2 Cure att~15 min 9 8 7 Cure at t~20 min 10 Cure at t~140 min 10 9 8 8 5 Cure att~260 min 10 9 8 7 Cure at t~3 days 10 9 9 9 9 GDL Adhesion N/A Samples2-5: Fragmented microlayer when removing GDL Cure under GDL @ 3 daysLiner Side N/A 9 9 4 4 GDL Side N/A 9 6 4 4 Cure ratings after 15 min in110 C. oven Cure under GDL Liner Side N/A 10 9 8 6 GDL Side N/A 10 9 8 6Cure rating scale 10 = Fully cured 5 = Skin on top of coating 1 = Nocure

Any suitable electrolyte membrane may be used in the practice of thepresent invention. Useful PEM thicknesses range between about 200 μm andabout 15 μm. Copolymers of tetrafluoroethylene (TFE) and a co-monomeraccording to the formula: FSO2-CF2-CF2-O—CF(CF3)-CF2-O—CF═CF2 are knownand sold in sulfonic acid form, i.e., with the FSO2-end group hydrolyzedto HSO3-, under the trade name NAFION® by DuPont Chemical Company,Wilmington, Del. NAFION® is commonly used in making polymer electrolytemembranes for use in fuel cells. Copolymers of tetrafluoroethylene (TFE)and a co-monomer according to the formula: FSO2-CF2-CF2-O—CF═CF2 arealso known and used in sulfonic acid form, i.e., with the FSO2-end grouphydrolyzed to HSO3-, in making polymer electrolyte membranes for use infuel cells. Most preferred are copolymers of tetrafluoroethylene (TFE)and FSO2-CF2CF2CF2CF2-O—CF═CF2, with the FSO2-end group hydrolyzed toHSO3-. Other materials suitable for PEM construction are described incommonly owned U.S. patent application Ser. No. 11/225,690 filed 13 Sep.2005 which is incorporated herein by reference.

In some embodiments, the catalyst layers may comprise Pt or Pt alloyscoated onto larger carbon particles by wet chemical methods, such asreduction of chloroplatinc acid. This form of catalyst is dispersed withionomeric binders and/or solvents to form an ink, paste, or dispersionthat is applied either to the membrane, a release liner, or GDL.

In some embodiments, the catalyst layers may comprise nanostructuredsupport elements bearing particles or nanostructured thin films (NSTF)of catalytic material. Nanostructured catalyst layers do not containcarbon particles as supports and therefore may be incorporated into verythin surface layers of the electrolyte membrane forming a densedistribution of catalyst particles. The use of nanostructured thin film(NSTF) catalyst layers allows much higher catalyst utilization thancatalyst layers formed by dispersion methods, and offer more resistanceto corrosion at high potentials and temperatures due to the absence ofcarbon supports. In some implementations, the catalyst surface area of aCCM may be further enhanced by using an electrolyte membrane havingmicrostructured features. Various methods for making microstructuredelectrolyte membranes and NSTF catalyst layers are described in thefollowing commonly owned patent documents which are incorporated hereinby reference: U.S. Pat. Nos. 4,812,352, 5,879,827, and 6,136,412 andU.S. patent application Ser. No. 11/225,690 filed Sep. 13, 2005 and Ser.No. 11/224,879, filed Sep. 13, 2005.

NSTF catalyst layers comprise elongated nanoscopic particles that may beformed by vacuum deposition of catalyst materials on to acicularnanostructured supports. Nanostructured supports suitable for use in thepresent invention may comprise whiskers of organic pigment, such as C.I.PIGMENT RED 149 (perylene red). The crystalline whiskers havesubstantially uniform but not identical cross-sections, and highlength-to-width ratios. The nanostructured support whiskers are coatedwith coating materials suitable for catalysis, and which endow thewhiskers with a fine nanoscopic surface structure capable of acting asmultiple catalytic sites.

The nanostructured support elements are coated with a catalyst materialto form a nanostructured thin film catalyst layer. According to oneimplementation, the catalyst material comprises a metal, such as aplatinum group metal. In one embodiment, the catalyst coatednanostructured support elements may be transferred to a surface of anelectrolyte membrane to form a catalyst coated membrane. In anotherembodiment, the catalyst coated nanostructured support elements maybeformed on a GDL surface.

The GDLs can be any material capable of collecting electrical currentfrom the electrode while allowing reactant gasses to pass through,typically a woven or non-woven carbon fiber paper or cloth. The GDLsprovide porous access of gaseous reactants and water vapor to thecatalyst and membrane, and also collect the electronic current generatedin the catalyst layer for powering the external load.

The GDLs may include a microporous layer (MPL) and an electrode backinglayer (EBL), where the MPL is disposed between the catalyst layer andthe EBL. EBLs may be any suitable electrically conductive poroussubstrate, such as carbon fiber constructions (e.g., woven and non-wovencarbon fiber constructions). Examples of commercially available carbonfiber constructions include trade designated “AvCarb P50” carbon fiberpaper from Ballard Material Products, Lowell, Mass.; “Toray” carbonpaper which may be obtained from ElectroChem, Inc., Woburn, Mass.;“SpectraCarb” carbon paper from Spectracorp, Lawrence, Mass.; “AFN”non-woven carbon cloth from Hollingsworth & Vose Company, East Walpole,Mass.; and “Zoltek” carbon cloth from Zoltek Companies, Inc., St. Louis,Mo. EBLs may also be treated to increase or impart hydrophobicproperties. For example, EBLs may be treated with highly-fluorinatedpolymers, such as polytetrafluoroethylene (PTFE) and fluorinatedethylene propylene (FEP).

The carbon fiber constructions of EBLs generally have coarse and poroussurfaces, which exhibit low bonding adhesion with catalyst layers. Toincrease the bonding adhesion, the microporous layer may be coated tothe surface of EBLs. This smoothens the coarse and porous surfaces ofEBLs, which provides enhanced bonding adhesion with some types ofcatalyst layers.

The foregoing description of the various embodiments of the inventionhas been presented for the purposes of illustration and description. Itis not intended to be exhaustive or to limit the invention to theprecise form disclosed. Many modifications and variations are possiblein light of the above teaching. It is intended that the scope of theinvention be limited not by this detailed description, but rather by theclaims appended hereto.

1. A method of making fuel cell membrane electrode assemblies (MEAs) viaa roll-to-roll process, comprising: transporting a web comprising asubgasketed catalyst coated membrane (CCM) layer and applying acrosslinkable resin to at least a subgasketed portion of the subgasketedCCM layer, the crosslinkable resin comprising a photocurable cationiccrosslinkable resin; subjecting an exposed surface of the crosslinkableresin to a photo curing process to initiate curing of the crosslinkableresin; terminating the photo curing process while the crosslinkableresin continues to cure in a partially cured state; transporting a webcomprising a gas diffusion layer (GDL) into adhering contact with apartially cured exposed surface of the crosslinkable resin of the CCMlayer so as to form an MEA layer; and producing, subsequent tosubstantial completion of crosslinkable resin curing, discrete MEAs fromthe MEA layer.
 2. The method of claim 1, comprising subjecting the GDL,partially cured crosslinkable resin, and CCM layer structure to athermal curing process to substantially complete curing of thecrosslinkable resin.
 3. The method of claim 1, wherein the webcomprising the CCM layer has a first surface and a second surface, andthe first and second surfaces are subjected to the subjecting,terminating, and transporting processes substantially concurrently. 4.The method of claim 1, wherein the web comprising the CCM layer has afirst surface and a second surface, and wherein: subjecting the exposedsurface of the crosslinkable resin to the photo curing process,terminating the photo curing process, and transporting the webcomprising the gas diffusion layer (GDL) into adhering contact with thepartially cured exposed surface of the crosslinkable resin is conductedduring a first phase for the first surface of the CCM layer; andsubjecting the exposed surface of the crosslinkable resin to the photocuring process, terminating the photo curing process, and transportingthe web comprising the gas diffusion layer (GDL) into adhering contactwith the partially cured exposed surface of the crosslinkable resin isconducted during a second phase for the second surface of the CCM layer.5. The method of claim 1, wherein subjecting the exposed surface of thecrosslinkable resin to the photo curing process comprises subjecting theexposed surface of the crosslinkable resin to an ultraviolet lightcuring process.
 6. The method of claim 1, wherein the crosslinkableresin comprises a cationically polymerizable monomer.
 7. The method ofclaim 6, wherein the cationically polymerizable monomer comprises anepoxide monomer.
 8. The method of claim 6, wherein the cationicallypolymerizable monomer comprises a vinyl ether monomer.
 9. The method ofclaim 6, wherein the cationically polymerizable monomer comprises anepoxide monomer and a vinyl ether monomer.
 10. A fuel cell membraneelectrode assembly (MEA), comprising: a catalyst coated membrane (CCM)comprising a first surface and a second surface, the first surfacecomprising an anode catalyst layer and the second surface comprising acathode catalyst layer; a subgasket provided about a peripheral regionof the CCM on the first and second surfaces; a crosslinked resinprovided on at least the subgasket of the first and second CCM surfaces,the crosslinked resin comprising a photocurable cationic crosslinkedresin; and a gas diffusion layer (GDL) adheringly sealed to thesubgasket of the first and second CCM surfaces via the crosslinkedresin.
 11. The assembly of claim 10, wherein the crosslinked resin is aphotocurable and thermally curable crosslinked resin.
 12. The assemblyof claim 10, wherein the crosslinked resin comprises a cationicallypolymerizable monomer.
 13. The assembly of claim 12, wherein thecationically polymerizable monomer comprises an epoxide monomer.
 14. Theassembly of claim 12, wherein the cationically polymerizable monomercomprises a vinyl ether monomer.
 15. The assembly of claim 12, whereinthe cationically polymerizable monomer comprises an epoxide monomer anda vinyl ether monomer.
 16. An apparatus for producing fuel cell membraneelectrode assemblies (MEAs), comprising: a first transport systemconfigured to move a web comprising a subgasketed catalyst coatedmembrane (CCM) layer; an application system configured to apply acrosslinkable resin to at least a subgasketed portion of the subgasketedCCM layer, the crosslinkable resin comprising a photocurable cationiccrosslinkable resin; a first curing apparatus configured to subject anexposed surface of the crosslinkable resin to a photo curing process toinitiate curing of the crosslinkable resin; a second transport systemconfigured to move a gas diffusion layer (GDL) into adhering contactwith a partially cured exposed surface of the crosslinkable resin of theCCM layer so as to form an MEA layer; and a converting system configuredto receive the MEA layer and produce a plurality of discrete MEAs fromthe MEA layer.
 17. The apparatus of claim 16, comprising a second curingapparatus configured to subject the GDL, partially cured crosslinkableresin, and CCM layer structure to a thermal curing process tosubstantially complete curing of the crosslinkable resin.
 18. Theapparatus of claim 16, wherein the application system comprises a rotaryscreen printing system.
 19. The apparatus of claim 16, wherein thesecond transport system is configured to move a web comprising the gasdiffusion layer into adhering contact with the partially cured exposedsurface of the crosslinkable resin.
 20. The apparatus of claim 16,wherein the application system is configured to apply a crosslinkableresin comprising a cationically polymerizable monomer to at least thesubgasketed portion of the subgasketed CCM layer.
 21. The apparatus ofclaim 20, wherein the cationically polymerizable monomer comprises anepoxide monomer.
 22. The apparatus of claim 20, wherein the cationicallypolymerizable monomer comprises a vinyl ether monomer.
 23. The apparatusof claim 20, wherein the cationically polymerizable monomer comprises anepoxide monomer and a vinyl ether monomer.